KR20110112525A - Post treatment technology and its formulation for electric thermal conductive carbon nanotube thin film - Google Patents

Abstract

The present invention is a method for greatly improving the properties of the carbon nanotube conductive film by performing a post-treatment process using a solution having a titanium alkoxide and magnesium alkoxide and a reaction initiation solution in the carbon nanotube conductive thin film. And compositions formed by this method. This method treats the carbon nanotube conductive film formed by various methods to treat a post-treatment solution composed of titanium alkoxide and magnesium alkoxide, and induces the decomposition of titanium alkoxide and magnesium alkoxide and the physical and chemical coupling reactions Therefore, it can be used in various parts / products where carbon nanotubes are applied because it effectively improves electrical characteristics.

Description

Post-treatment technology and its formulation for electric thermal conductive carbon nanotube thin film

The present invention relates to a post-treatment process method and composition thereof of an electrically thermally conductive carbon nanotube thin film, and more particularly, to physical, chemical and electrical properties of an electrically or thermally conductive carbon nanotube thin film on a substrate or surface treated substrate. A post-treatment process method of coating a composition that can be improved and the composition formed thereby.

The conductive thin film including carbon nanotubes may be coated on a substrate by substituting hydrophilic functional groups on the carbon nanotubes or forming a water-dispersible carbon nanotube solution using an aqueous surfactant, or using carbon nanotubes using an organic solvent. It is formed by a method of dispersing the coating.

The above-described techniques can obtain a carbon nanotube conductive thin film by a relatively simple method, but it is difficult to apply to various products due to low electrical conductivity and weak environmental stability. Existing prior arts to solve this problem, a method for improving the physical properties of the conductive thin film by replacing a functional group on the carbon nanotubes, a method for adding a specific material to improve the adhesion and durability to the carbon nanotube dispersion solution, Pretreatment coating of a material capable of inducing a chemical reaction or strong physical interaction with the substrate, and a method of top-coating with a specific material after forming a carbon nanotube film.

The above-described methods have the following characteristics according to their respective methods.

The method of substituting functional groups on carbon nanotubes secures the properties of carbon nanotube conductive thin films by inducing chemical / physical bonds between carbon nanotubes and between substrates and carbon nanotubes by substituting specific functional groups for carbon nanotubes chemically. can do. However, this method may cause a problem of reducing the conductivity of the carbon nanotubes in the process of introducing functional groups into the carbon nanotubes, and the environmental stability is still weak because the carbon nanotubes are exposed to the outside air.

In the case of adding specific chemicals to the carbon nanotube dispersion solution to improve the durability, it is possible to efficiently form a durable conductive film through a single coating process. However, this method may be difficult to maintain the dispersibility of the carbon nanotube dispersion solution, and the problem of reduced conductivity, light transmittance and haze generation due to the thin film remaining of the additive material.

Substrate surface treatment and pre-treatment coating method can obtain high conductivity characteristics while showing relatively excellent thin film durability, but due to external exposure of carbon nanotubes may be weak to external forces and weak environmental safety.

The method of securing the properties of the conductive film by top-coating is advantageous in terms of performance deterioration and environmental stability by the external force, but the conductivity of the conductive film may be reduced due to the top-coating.

Accordingly, an object of the present invention in view of the above-described conventional problems is a post-treatment process composition material and reaction including titanium alkoxide and magnesium alkoxide in a conductive film including carbon nanotubes. By providing a simple post-treatment process using the starting material to provide a post-treatment process method and composition that can efficiently improve the chemical resistance, adhesion, and electrical properties of the conductive thin film.

The composition formed by the electrically thermally conductive carbon nanotube thin film post-treatment process method according to a preferred embodiment of the present invention for achieving the object as described above, the substrate; A carbon nanotube conductive film formed on the substrate; And a post-treatment solution including at least one titanium alkoxide and at least one magnesium alkoxide on the conductive layer, and formed of carbon nanotubes, titanium, and magnesium. A compound film composed of a compound).

The compound film is made of titanium, magnesium hydrate and oxide.

The aftertreatment solution composition is characterized in that the metal (oxygen) -atomic atom-organic substituent (R) structure.

The metal is titanium and magnesium, characterized in that at least one of the metal methoxide, metal ethoxide, metal propoxide, metal isopropoxide, metal butoxide, and metal pentoxide (metal alkoxide) according to the form of the organic substituent. .

The concentration of the titanium alkoxide and the magnesium alkoxide is characterized in that less than 50 wt%.

The compound film is characterized in that formed to a thickness of 0.1nm to 500nm.

Formed on the compound film is characterized in that it further comprises a polymer film made of a polymer.

The substrate is characterized by using any one of glass, quartz, glass wafers, silicon wafers, transparent and opaque plastic substrates, transparent and opaque polymer films.

The conductive layer is characterized in that at least one of a single-walled carbon nanotubes, a functionalized single-walled carbon nanotubes, a double-walled carbon nanotubes, a functionalized double-walled carbon nanotubes, multi-walled carbon nanotubes, functionalized multi-walled carbon nanotubes are used It is done.

According to a preferred embodiment of the present invention, an electrothermally conductive carbon nanotube thin film post-processing method for achieving the object described above may include preparing a substrate and conducting a conductive solution using a carbon nanotube dispersion solution on the substrate. Carbon nanotubes, titanium and titanium by using a post-treatment solution including a process of forming a film and at least one titanium alkoxide and at least one magnesium alkoxide on the conductive film. A process of forming a compound film made of a compound containing magnesium is included.

The compound film is made of titanium, magnesium hydrate and oxide.

The aftertreatment solution composition is characterized in that the metal (oxygen) -atomic atom-organic substituent (R) structure.

The titanium alkoxide is characterized by using at least any one of titanium methoxide, titanium ethoxide, titanium propoxide, titanium isopropoxide, titanium butoxide and titanium pentoxide according to the alkoxide functional group.

The magnesium alkoxide is characterized by using at least one of magnesium methoxide, magnesium ethoxide, magnesium propoxide, magnesium isopropoxide, magnesium butoxide and magnesium pentoxide.

The concentration of the titanium alkoxide and the magnesium alkoxide is characterized in that less than 50 wt%.

The process of forming the compound film may include dip coating, spray coating, spin coating, solution casting, dropping, and rolling the post-treatment solution on the conductive film. Roll coating, gravure coating, bar coating (bar coating) characterized in that the coating by any one method.

After the compound film is formed, a step of inducing a chemical reaction of the post-treatment coating composition may include dip coating and spraying after the post-treatment solution is coated with at least one reaction starting solution selected from water, alcohol, acid, and base. ) Coating, spin coating, solution casting, dropping, roll coating, gravure coating, or bar coating.

The method may further include forming a polymer film using a polymer material on the compound film. Here, the process of forming the polymer film is a dip coating, spray coating, spin coating, solution casting, dropping, roll coating on the compound film It characterized in that the coating of the single or different types of polymer material by at least one method, gravure coating, bar coating (bar coating).

After the preparation process, before the process of forming the conductive film, Piranha solution treatment, acid treatment, base treatment, plasma treatment, atmospheric pressure plasma treatment, ozone treatment, UV treatment, SAM (self assembled monolayer) on the substrate Treatment, and further comprising the step of performing a surface treatment using at least one of the polymer or monomolecular coating method.

The carbon nanotube dispersion solution is produced by using an aqueous surfactant and an organic solvent. The aqueous surfactant may be selected from at least one of SDBS, SDS, LDS, CTAB, DTAB, PVP, Triton X-series, Brij-series, Tween-series, poly (acrylic acid), and polyvinyl alcohol. Characterized in that. In addition, the organic solvent is characterized by using at least one selected from NMP, DMF, DCE, and THF.

Forming the conductive film may include dip coating, spray coating, spin coating, solution casting, dropping, and rolling the carbon nanotube dispersion solution on the substrate. (roll) coating, characterized in that the coating using any one of the methods such as gravure coating.

The present invention provides a method for greatly improving the electrical conductivity and environmental stability of a conductive thin film including carbon nanotubes by coating a post-treatment solution on a previously formed conductive thin film and contacting the reaction initiation solution. The aftertreatment solution contains titanium alkoxide and magnesium alkoxide, and the compound film formed in contact with the reaction initiation solution after coating the aftertreatment solution greatly improves the chemical resistance and environmental stability of the conductive film while simultaneously improving the electrical conductivity of the conductive thin film. There is this.

In particular, this method can be easily applied to conductive thin films formed by various methods, and can effectively improve the physical properties of the thin films. To be applied.

1 and 2 are views for explaining the composition according to the post-treatment of the electrically thermally conductive carbon nanotube thin film according to an embodiment of the present invention.
3 is a flow chart for explaining a method of post-processing an electrically thermally conductive carbon nanotube thin film according to an embodiment of the present invention.
4 to 7 are views for explaining a method of post-processing the electrically thermally conductive carbon nanotube thin film according to an embodiment of the present invention.
8 is a flowchart illustrating a method of post-processing an electrically thermally conductive carbon nanotube thin film according to a first embodiment of the present invention.
9 is a flowchart illustrating a method of post-processing an electrically thermally conductive carbon nanotube thin film according to a second embodiment of the present invention.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings. It should be noted that in the following description, only parts necessary for understanding the operation according to the present invention will be described, and descriptions of other parts will be omitted so as not to distract from the gist of the present invention.

First, the composition according to the post-treatment of the electrically thermally conductive carbon nanotube thin film according to the embodiment of the present invention will be described. 1 and 2 are views for explaining the composition according to the post-treatment of the electrically thermally conductive carbon nanotube thin film according to an embodiment of the present invention.

Referring to Figure 1, the composition according to the post-heat treatment of the electrically conductive carbon nanotube thin film according to an embodiment of the present invention is formed on the substrate 100, according to the post-treatment process, the carbon nanotube conductive thin film (hereinafter, With a compound film (hereinafter, abbreviated as "compound film") 300 formed as a composite of carbon nanotube-titanium-magnesium compound on the "conductive film" (200) Is done. That is, as illustrated, the substrate 100, the conductive film 200, and the compound film 300 have a stacked structure.

The substrate 100 may use any one of glass, quartz, glass wafers, silicon wafers, transparent and opaque plastic substrates, transparent and opaque polymer films, and metals. At least one of Piranha solution treatment, acid treatment, base treatment, plasma treatment, atmospheric pressure plasma treatment, ozone treatment, UV treatment, SAM (self assembled monolayer) treatment, and polymer or monomolecular coating method are applied to the substrate 100. One method can be used to perform surface treatment.

The conductive film 200 is formed by producing a carbon nanotube dispersion solution and then coating the dispersion solution on the upper surface of the substrate 100. The conductive film 200 is formed of at least one of single-walled carbon nanotubes, functionalized single-walled carbon nanotubes, double-walled carbon nanotubes, functionalized double-walled carbon nanotubes, multi-walled carbon nanotubes, and functionalized multi-walled carbon nanotubes. .

The carbon nanotube dispersion solution may use an aqueous surfactant or may generate a dispersion solution using an organic solvent. When using an aqueous surfactant, using an aqueous surfactant such as SDBS, SDS, LDS, CTAB, DTAB, PVP, Triton X-series, Brij-series, Tween-series, poly (acrylic acid), polyvinyl alcohol, etc. desirable. In addition, when using an organic solvent, it is preferable to use the organic solvent comprised from NMP, DMF, DCE, THF, etc. On the other hand, in addition to the above-described aqueous surfactant or organic solvent can be produced carbon nanotube dispersion solution by various other methods.

After the carbon nanotube dispersion solution is generated, the conductive film 200 is formed by coating the dispersion solution on the upper surface of the substrate 100. In this case, the coating may be any one of dip coating, spray coating, spin coating, solution casting, dropping, roll coating, and gravure coating. It is preferably carried out using the method of.

The compound film 300 is formed by generating a post-treatment solution and then coating the post-treatment solution on the conductive film 200 and contacting the reaction initiation solution. The compound film 300 is preferably formed to a thickness of 0.1nm to 500nm.

The post-treatment solution includes titanium alkoxide and magnesium alkoxide, and the post-treatment solution is coated on the conductive film 200 to react with the reaction initiation solution to form the compound film 300. It is possible to improve the physical properties of the 200).

The aftertreatment solution composition is a material having a metal-oxygen atom-R structure, where metal is titanium or magnesium and R is an organic substituent. Titanium alkoxide may be selected from at least one of titanium methoxide, titanium ethoxide, titanium propoxide, titanium isopropoxide, titanium butoxide and titanium pentoxide depending on the alkoxide functional group. Magnesium alkoxide may be selected from at least one of magnesium methoxide, magnesium ethoxide, magnesium propoxide, magnesium isopropoxide, magnesium butoxide and magnesium pentoxide.

In the post-treatment process described above, some or all of the organic substituents R are decomposed, removed, and bonded to each other to form a compound film 300 which is a thin film of carbon nanotube composite including titanium and magnesium.

The post-treatment solution contains at least 50 wt% of titanium alkoxide and at least 50 wt% of magnesium alkoxide, and the solvents include alcohols such as methanol, ethanol, propanol, isopropanol, butanol, organic solvents, and the like. Mixtures of these may be used.

Post-treatment process solutions containing titanium alkoxide and magnesium alkoxide may be prepared by dip coating, spray coating, spin coating, solution casting, dropping, roll coating, The conductive film 200 is coated by any one or more of gravure coating and bar coating.

After the post-treatment solution is coated on the conductive film, the initiation solution is dip coated, spray coated, spin coated, solution casting, dropping, roll coating. The compound film 300, which is a carbon nanotube composite thin film including titanium and magnesium, is formed by at least one of gravure coating and bar coating.

 The reaction starting solution may be mainly used as a material capable of reacting with the aftertreatment solution. In addition, alcohol, acid, base, and the like may be used.

The compound film 300, which is the carbon nanotube composite thin film formed by the above method, is mainly composed of titanium, magnesium hydrate, and oxide, and has the adhesiveness, environmental stability, It shows the result of improving electric conductivity.

In addition, by repeatedly applying the above-described post-treatment process, titanium and magnesium compounds may be additionally formed in the conductive film 200 including carbon nanotubes, thereby improving physical properties of the conductive film 200.

Meanwhile, referring to FIG. 2, the polymer film 400 may be further formed on the compound film 300 formed by the method described above.

That is, the compound film 300 may be further contacted with a polymer solution having water, alcohol, acid, base, -OH, or -COOH functional group to form the polymer film 400 and at the same time promote the reaction of the post-treatment solution component. have. As such, durability may be improved by using a method of additionally coating a polymer material on the compound film 300, which is a carbon nanotube composite thin film including titanium and magnesium, formed by the method according to the embodiment of the present invention.

In addition, carbon nanotubes are formed by repeating a post-treatment process of forming the compound film 300 using a solution containing titanium alkoxide and magnesium alkoxide, or by repeating a polymer coating process of forming the polymer film 400. Durability of the composite thin film can be significantly improved.

In particular, the carbon nanotube composite film formed by the method of the present invention showed an improvement in electrical conductivity as compared to before the post-treatment process, which showed that the sheet resistance value of the composite thin film was reduced by 15% or more.

Next, a method of post-processing an electrically thermally conductive carbon nanotube thin film according to an embodiment of the present invention will be described.

Figure 3 is a flow chart for explaining the electrothermal conductive carbon nanotube thin film post-treatment process method according to an embodiment of the present invention, Figures 4 to 7 is an electrothermal conductive carbon nanotube thin film post-treatment according to an embodiment of the present invention It is a figure for demonstrating a process method.

First, in step S301 to prepare a substrate 100 as shown in FIG. The substrate 100 may use any one of glass, quartz, glass wafers, silicon wafers, transparent and opaque plastic substrates, transparent and opaque polymer films, and metals.

When the substrate 100 is provided, surface treatment may be performed on the substrate 100 in operation S303. Surface treatment is at least one of Piranha solution treatment, acid treatment, base treatment, plasma treatment, atmospheric pressure plasma treatment, ozone treatment, UV treatment, self assembled monolayer (SAM) treatment, and polymer or monomolecular coating method. It can be performed using. Performing the surface treatment of the substrate 100 using the above-described method is called pretreatment, and such pretreatment may be omitted without performing or pretreating the pretreatment according to the type of the substrate 100.

Then, in step S305 to form a conductive film 200 using a carbon nanotube dispersion solution on the substrate 100. 5 illustrates a state in which the conductive film 200 is formed on the substrate 100.

The carbon nanotube dispersion solution may use an aqueous surfactant or may generate a dispersion solution using an organic solvent. When using an aqueous surfactant, using an aqueous surfactant such as SDBS, SDS, LDS, CTAB, DTAB, PVP, Triton X-series, Brij-series, Tween-series, poly (acrylic acid), polyvinyl alcohol, etc. desirable. In addition, when using an organic solvent, it is preferable to use the organic solvent comprised from NMP, DMF, DCE, THF, etc. On the other hand, in addition to the above-described aqueous surfactant or organic solvent can be produced carbon nanotube dispersion solution by various other methods.

After the carbon nanotube dispersion solution is generated, the conductive film 200 is formed by coating the dispersion solution on the upper surface of the substrate 100. In this case, the coating may be any one of dip coating, spray coating, spin coating, solution casting, dropping, roll coating, and gravure coating. It is preferably carried out using the method of.

In particular, in the conductive film 200 including the carbon nanotubes formed as described above, the carbon nanotubes are single-walled carbon nanotubes, functionalized single-walled carbon nanotubes, double-walled carbon nanotubes, functionalized double-walled carbon nanotubes, multiple Carbon nanotubes of at least one kind of wall carbon nanotubes and functionalized multi-walled carbon nanotubes may be used.

Then, the dispersant is washed with water in step S307, and dried in step S309.

Subsequently, the carbon nanotube conductive layer 200 is subjected to a post-treatment process in step S311 to form the compound layer 300, which is a composite of carbon nanotube-titanium-magnesium compound, on the conductive layer 200. 6 illustrates a state in which the compound film 300 is formed on the conductive film 200 according to the post-treatment process. The post-treatment process is to form a compound film 300 by coating the post-treatment solution on the conductive film 200.

The aftertreatment solution (or aftertreatment process composition) may include titanium alkoxide and magnesium alkoxide, and may improve physical properties of the conductive layer 200 by coating the aftertreatment solution on the conductive layer 200 and contacting the reaction initiation solution. .

The aftertreatment solution composition is a material having a metal-oxygen atom-R structure, where metal is titanium or magnesium and R is an organic substituent. Titanium alkoxide may be selected from at least one of titanium methoxide, titanium ethoxide, titanium propoxide, titanium isopropoxide, titanium butoxide and titanium pentoxide depending on the alkoxide functional group. Magnesium alkoxide may be selected from at least one of magnesium methoxide, magnesium ethoxide, magnesium propoxide, magnesium isopropoxide, magnesium butoxide and magnesium pentoxide.

In the post-treatment process described above, some or all of the organic substituents R are decomposed, removed, and bonded to each other to form a compound film 300 which is a thin film of carbon nanotube composite including titanium and magnesium.

The aftertreatment solution contains at least one kind of titanium alkoxide and at least one kind of magnesium alkoxide, and the concentration of each of the titanium alkoxide and magnesium alkoxide component materials is preferably 50 wt% or less. Here, as the solvent, alcohols such as methanol, ethanol, propanol, isopropanol, butanol, organic solvents and mixtures thereof may be used.

Post-treatment process solutions containing titanium alkoxide and magnesium alkoxide may be prepared by dip coating, spray coating, spin coating, solution casting, dropping, roll coating, It is coated by any one or more of gravure coating or bar coating.

The initiation solution is followed by dip coating, spray coating, spin coating, solution casting, dropping, roll coating and gravure coating after coating of the post-treatment process solution. , By coating by any one or more of the bar coating (bar coating) to form a compound film 300 which is a carbon nanotube composite thin film containing titanium and magnesium.

The compound film 300 formed through the above-described post-treatment solution mainly consists of a hydrate and an oxide of titanium and magnesium.

Next, in step S313 to form a polymer film 400 on the compound film (300). 7 illustrates a state in which the polymer film 400 is formed on the compound film 300. The step S213 is optionally performed, and the compound film 300 is further contacted with a polymer solution having water, alcohol, acid, base, -OH or -COOH functional group to form the polymer film 400 and at the same time a post-treatment process solution Can promote the reaction of the components.

According to the embodiment of the present invention as described above, when a solution in which titanium alkoxide and magnesium alkoxide material are mixed is applied to the carbon nanotube conductive thin film, physical properties of the conductive film 200 may be improved. On the other hand, when the titanium alkoxide and magnesium alkoxide, which are the constituents of the present invention, are dissolved in separate solvents and applied separately, the same results as those of the present invention could not be obtained. In the case of titanium alkoxide solution, white particles were formed in the carbon nanotube film after drying, resulting in a light transmittance, and the surface resistance was increased when magnesium alkoxide solution was applied.

Next, specific embodiments of the present invention will be described, and thus the effects of the present invention will be described.

First embodiment

8 is a flowchart illustrating a method of post-processing an electrically thermally conductive carbon nanotube thin film according to a first embodiment of the present invention.

4 to 6 and 8, in step S801, a substrate 100 is prepared as shown in FIG. 4. Here, the substrate 100 is a soda lime glass (sodalime glass) substrate.

When the substrate 100 is provided, surface treatment may be performed on the substrate 100 in operation S803 according to the type of the substrate.

Then, the conductive film 200 is formed on the substrate 100 using the carbon nanotube dispersion solution in step S805. 3 shows the conductive film 200 formed on the substrate 100. Here, the carbon nanotube dispersion solution is prepared by adding a sodium dodecylbenzenesulfonate (SDBS) dispersant to a single-wall carbon nanotube, using an ultrasonic disperser (Ultrasound Homogenizer), and spraying using the produced carbon nanotube dispersion solution. The conductive film 200 was formed by coating the upper surface of the substrate 100 with a coating device.

Then, the process of washing the dispersant with water in step S807. Then, dry at room temperature for 60 minutes in step S809. After drying, the sheet resistance of the carbon nanotube conductive film 200 was measured and has a value of 584 Ω / sq.

Subsequently, a post-treatment process of the carbon nanotube conductive film 200 is performed in step S811 to form a compound film 300, which is a composite of carbon nanotube-titanium-magnesium compound, on the conductive film 200. 4 illustrates a state in which the compound film 300 is formed on the conductive film 200. The compound film 300 is formed by coating the post-treatment solution on the conductive film 200 and contacting the reaction initiation solution. The post-treatment solution (or post-treatment process composition) includes titanium alkoxide and magnesium alkoxide, and the conductive film It is possible to improve the physical properties of the conductive film by coating the post-treatment solution to 200 and contacting the reaction starting solution. The aftertreatment solution composition is a material having a metal-oxygen atom-R structure, where metal is titanium or magnesium and R is an organic substituent. In the post-treatment process described above, some or all of the organic substituents R are decomposed, removed, and bonded to each other to form a compound film 300 which is a thin film of carbon nanotube composite including titanium and magnesium.

Here, the post-treatment solution used in the post-treatment process is produced by mixing 5 ml of ethanol solution of 1 wt% titanium ethoxide and methanol solution of 0.5 wt% magnesium methoxide, respectively. Thereafter, the compound film 300 is coated by spray coating on the conductive film 200 of the substrate 100 on which the conductive film 200 is formed using the generated post-treatment solution and dip coating water. Form. Then, it is dried for 2 hours at room temperature in step S813. After this drying, the measured sheet resistance had a value of 502 dl / sq. As such, it can be seen that the sheet resistance was reduced by 82 mA / sq.

In order to evaluate chemical resistance of the conductive film 200 including the carbon nanotube-titanium-magnesium compound formed by the above-described method, the specimen coated with the conductive film 200 may be acetone, toluene, Soak for 10 minutes in isopropyl alcohol (isopropylalcohol), methanol (methanol), 1-methyl pyrrolidone (1-methyl prrolidone). The specimen was washed with water and dried for 60 minutes to measure the sheet resistance change of the composite conductive film 200 to obtain the results as shown in Table 1 below.

Chemical resistance evaluation No post-processing Post-processing process Initial sheet resistance
(Ω / aq) Surface resistance after test
(Ω / sq) Initial surface resistance
(Ω / aq) Surface resistance after test
(Ω / sq) acetone 575  598 510 504 ethanol 580 600 485 492 toluene 640 645 554 565 isopropyl
alcohol 650 665 550 547 NMP 640 730 580 595

In addition, to evaluate the environmental stability, the change in sheet resistance was measured after storing for 240 hours at a relative humidity of 90 ° and a temperature of 60 ° C., and a 90 ° peel test was conducted using a “3M magic tape”. The result of the following <Table 2> was obtained.

Environmental stability evaluation No post-processing Post-processing process Initial sheet resistance
(Ω / aq) Surface resistance after test
(Ω / sq) Initial surface resistance
(Ω / aq) Surface resistance after test
(Ω / sq) Heat / humidity
resistance
(240hr at 60 ℃)
664
1368
568
679 90 ° Peel test
(3M magic tape,
Cat. 122A)
655
2014
524
590

Second embodiment

9 is a flowchart illustrating a method of post-processing an electrically thermally conductive carbon nanotube thin film according to a second embodiment of the present invention.

4 to 7 and 9, in step S901, a substrate 100 is prepared as shown in FIG. 4. Here, the PET substrate 100 was used. Then, the conductive film 200 is formed of carbon nanotubes using the carbon nanotube dispersion solution on the substrate 100 in step S903. Here, the dispersion solution is produced by adding a sodium dodecylbenzenesulfonate (SDBS) dispersant to the single-walled carbon nanotubes and using an ultrasonic disperser (Ultrasound Homogenizer). In addition, the conductive film 200 is produced by coating the upper surface of the substrate 100 with a spray coating apparatus using a dispersion solution. Then, the dispersant is removed by performing a washing process with water in step S905. Then, dried at room temperature for 60 minutes in step S907. The sheet resistance of the carbon nanotube conductive film 200 measured after drying has a value of 582 Ω / sq.

Subsequently, a post-treatment process of the carbon nanotube conductive film 200 is performed in step S909 to form a compound film 300 which is a thin film of a carbon nanotube-titanium-magnesium compound. 6 illustrates a state in which the compound film 300 is formed on the conductive film 200. The compound film 300 is formed by coating the post-treatment solution on the conductive film 200 and contacting the reaction initiation solution. The post-treatment solution (or post-treatment process composition) may include titanium alkoxide and magnesium alkoxide, and may be in contact with the reaction initiation solution to improve the physical properties of the conductive film 200 by coating the post-treatment solution on the conductive film 200. . The aftertreatment solution is a material having a metal-oxygen atom-R structure, where metal is titanium or magnesium and R is an organic substituent. In the post-treatment process described above, some or all of the organic substituents R are decomposed, removed, and bonded to each other to form a compound film 300 which is a thin film of carbon nanotube composite including titanium and magnesium. Here, the post-treatment solution is produced by mixing 5 ml of ethanol solution of 1 wt% titanium ethoxide and methanol solution of 0.5 wt% magnesium methoxide, respectively. The conductive film 200 is coated by a dip coating method using such a post-treatment solution, and dip is coated with water to form a compound film 300 made of a carbon nanotube-titanium-magnesium compound. Subsequently, as shown in FIG. 7 in step S911, the polymer film 400 is formed on the compound film 300. The polymer film 400 is formed by spray coating the compound film 300 using a 0.5 wt% polyacrylic acid aqueous solution. Then, it is dried for 3 hours in step S913. The sheet resistance of the composite thin film including the carbon nanotubes has a measurement result of 473 Ω / sq.

For the chemical resistance evaluation of the conductive film 200 including the carbon nanotube-titanium-magnesium compound formed by the method according to the second embodiment, the specimen is acetone, toluene, isopropylalcohol , Soak for 10 minutes in methanol (methanol), 1-methyl pyrrolidone (1-methyl prrolidone), and then washed with water and dried for 60 minutes to measure the sheet resistance change of the conductive film 200 and the following <Table 3> and The same result was obtained.

Chemical resistance evaluation No post-processing Post-processing process Initial sheet resistance
(Ω / aq) Surface resistance after test
(Ω / sq) Initial surface resistance
(Ω / aq) Surface resistance after test
(Ω / sq) acetone 575  598 568 556 ethanol 584 606 598 609 toluene 641 647 577 578 isopropyl
alcohol 658 665 610 625 NMP 640 732 565 576

In addition, to evaluate the environmental stability, the change in sheet resistance was measured for 240 hours at a relative humidity of 90 ° and a temperature of 60 ° C., and a 90 ° peel test was conducted using a “3M magic tape”. The following results were obtained as shown in Table 4.

Environmental stability evaluation No post-processing Post-processing process Initial sheet resistance
(Ω / aq) Surface resistance after test
(Ω / sq) Initial surface resistance
(Ω / aq) Surface resistance after test
(Ω / sq) Heat / humidity
resistance
(240hr at 60 ℃)
672
1122
545
589 90 ° Peel test
(3M magic tape,
Cat. 122A)
634
1902
568
565

The composition formed by the electrothermally conductive carbon nanotube thin film post-treatment process method formed by the method of the present invention as described above is of a high quality with improved physical properties, and the transparent electrode, surface heating element, electrostatic control by excellent durability and high conductivity And it can be applied to various parts such as absorbent, electromagnetic shielding film, heat radiation material.

In particular, although the content of the present invention has been described as described above, the scope of the present invention is not limited to the above content. The present invention can be applied to all of the conductive film 200 formed in various ways according to the pretreatment method, carbon nanotube type, carbon nanotube coating method.

As described above, in the detailed description of the present invention has been described with respect to specific embodiments, various modifications are possible without departing from the scope of the invention. Therefore, the scope of the present invention should not be limited to the described embodiments, but should be determined not only by the claims below, but also by the equivalents of the claims.

100: substrate
200: conductive film
300 compound film
400: polymer membrane

Claims (24)

In the composition formed by the electrically thermally conductive carbon nanotube thin film post-treatment process method,
Board;
A carbon nanotube conductive film formed on the substrate; And
A carbon nanotube, titanium and An electrothermally conductive carbon nanotube thin film post-treatment process method comprising a compound film made of a compound of magnesium (magnesium). The method of claim 1,
The compound film is a composition formed by an electrothermally conductive carbon nanotube thin film post-treatment process comprising a hydrate and oxide of titanium and magnesium. The method of claim 1,
The post-treatment solution composition is a composition formed by an electrothermally conductive carbon nanotube thin film post-treatment process, characterized in that the metal (oxygen) -organic substituent (R) structure. The method of claim 3,
The metal is titanium and magnesium, and at least one of metal methoxide, metal ethoxide, metal propoxide, metal isopropoxide, metal butoxide, and metal pentoxide, depending on the form of the organic substituent, characterized in that the metal alkoxide (metal alkoxide) A composition formed by an electrically thermally conductive carbon nanotube thin film post-treatment process method. The method of claim 1,
Wherein the concentration of the titanium alkoxide and the magnesium alkoxide is 50 wt% or less, wherein the composition is formed by an electrothermally conductive carbon nanotube thin film post-treatment process method. The method of claim 1, wherein the compound film
The composition formed by the electrothermally conductive carbon nanotube thin film post-treatment process method characterized in that formed to a thickness of 0.1nm to 500nm. The method of claim 1,
The composition formed by the electrothermally conductive carbon nanotube thin film post-treatment process is formed on the compound film and further comprises a polymer film made of a polymer. The electrically thermally conductive carbon nanotube thin film of claim 1, wherein the substrate is made of any one of glass, quartz, glass wafer, silicon wafer, transparent and opaque plastic substrate, and transparent and opaque polymer film. A composition formed by a post treatment process method. The method of claim 1, wherein the conductive film,
At least one of single-walled carbon nanotubes, functionalized single-walled carbon nanotubes, double-walled carbon nanotubes, functionalized double-walled carbon nanotubes, multi-walled carbon nanotubes, and functionalized multi-walled carbon nanotubes is used. A composition formed by a thermally conductive carbon nanotube thin film post-treatment process method. In the thermally conductive carbon nanotube thin film post-treatment process method,
The process of preparing a substrate,
Forming a conductive film using a carbon nanotube dispersion solution on the substrate;
Carbon nanotubes, titanium and magnesium using a post-treatment solution and a reaction initiation solution containing at least one titanium alkoxide and at least one magnesium alkoxide on the conductive layer An electrothermally conductive carbon nanotube thin film post-treatment process comprising the step of forming a compound film made of a compound containing magnesium). The method of claim 10, wherein the compound film
An electrically thermally conductive carbon nanotube thin film post-treatment process comprising titanium, magnesium hydrate and oxide. The method of claim 10,
The post-treatment solution composition is an electrothermally conductive carbon nanotube thin film post-treatment process characterized in that the metal (oxygen) -organic substituent (R) structure. The method of claim 10, wherein the titanium alkoxide is
According to the alkoxide functional group, at least one of titanium methoxide, titanium ethoxide, titanium propoxide, titanium isopropoxide, titanium butoxide, and titanium pentoxide is selected and used. The method of claim 10, wherein the magnesium alkoxide is
An electrothermally conductive carbon nanotube thin film post-treatment process comprising at least one of magnesium methoxide, magnesium ethoxide, magnesium propoxide, magnesium isopropoxide, magnesium butoxide and magnesium pentoxide. The method of claim 10,
And the titanium alkoxide and the magnesium alkoxide have a concentration of 50 wt% or less.
The method of claim 10,
The reaction initiation solution may react with the aftertreatment coating composition. A post-treatment process method comprising at least one of alcohols, acids and bases. The process of claim 10, wherein the forming of the compound film is performed.
Dip coating, spray coating, spin coating, solution casting, dropping, roll coating, gravure coating, on the conductive film The coating may be carried out by any one of bar coating, and then the reaction starting solution may be dip coated, spray coated, spin coated, solution casting, or doping. Electrothermal thermal conductive carbon nanotube thin film post-treatment process method characterized in that the coating by any one method of dropping), roll (roll) coating, gravure coating, bar coating (bar coating). The method of claim 10,
An electrothermally conductive carbon nanotube thin film post-treatment method further comprising forming a polymer film on the compound film using a polymer material. The process of claim 18, wherein the forming of the polymer film
Dip coating, spray coating, spin coating, solution casting, dropping, roll coating, gravure coating, bar coating on the compound film The thermally conductive carbon nanotube thin film post-treatment method of claim 1, wherein the single or different types of polymer materials are coated by at least one method. The method of claim 10, after the preparing process, before the forming of the conductive film,
Piranha solution treatment, acid treatment, base treatment, plasma treatment, atmospheric pressure plasma treatment, ozone treatment, UV treatment, SAM (self assembled monolayer) treatment, and polymer or monomolecular coating method on the substrate The electrothermally conductive carbon nanotube thin film post-treatment process method further comprising the step of performing a surface treatment using. The method of claim 10,
The carbon nanotube dispersion solution is an electrothermally conductive carbon nanotube thin film post-treatment process characterized in that it is produced using an aqueous surfactant and an organic solvent. The method of claim 21,
The aqueous surfactant is selected from at least one of SDBS, SDS, LDS, CTAB, DTAB, PVP, Triton X-series, Brij-series, Tween-series, poly (acrylic acid), and polyvinyl alcohol. An electrically thermally conductive carbon nanotube thin film post-treatment process method. The method of claim 21,
The organic solvent is NMP, DMF, DCE, and THF at least one selected from the thermally conductive carbon nanotube thin film post-treatment process characterized in that used. The process of claim 10, wherein the forming of the conductive film is performed.
Dip coating, spray coating, spin coating, solution casting, dropping, roll coating, gravure coating of the carbon nanotube dispersion solution on the substrate Electrothermal thermally conductive carbon nanotube thin film post-treatment process method characterized in that the coating by using any one of the methods.

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